Structure of Zinc and Nickel Histidine Complexes in Solution Revealed by Molecular Dynamics and Raman Optical Activity

0560611 - ÚOCHB 2023 RIV DE eng J - Journal Article
Hudecová, Jana - Kapitán, J. - Dračínský, Martin - Michal, P. - Profant, V. - Bouř, Petr
Structure of Zinc and Nickel Histidine Complexes in Solution Revealed by Molecular Dynamics and Raman Optical Activity.
Chemistry - A European Journal. Roč. 28, č. 59 (2022), č. článku e202202045. ISSN 0947-6539. E-ISSN 1521-3765
R&D Projects: GA ČR(CZ) GA22-04669S; GA ČR(CZ) GA22-15374S; GA MŠMT(CZ) EF16_019/0000729
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61388963
Keywords : density functional calculations * histidine * metal complexes * molecular dynamics * Raman optical activity * Raman spectroscopy
OECD category: Physical chemistry
Impact factor: 4.3, year: 2022
Method of publishing: Limited access
https://doi.org/10.1002/chem.202202045

The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis(2) complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis(2) is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems.
Permanent Link: https://hdl.handle.net/11104/0333475